CN103143336A - Regeneration method of activated carbon catalyst used for preparing glyphosate - Google Patents
Regeneration method of activated carbon catalyst used for preparing glyphosate Download PDFInfo
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- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a regeneration method of an activated carbon catalyst used for preparing glyphosate. The regeneration method comprises a solvent elution step and/or a heat treatment step, wherein the solvent elution step refers to treating inactivated activated carbon catalyst for 4-24 hours in a refluxing condition by using a water solution with alkaline or reducing inorganic substance or an organic solvent with alkalinity or reducibility; and the heat treatment step refers to high-temperature roasting to-be-treated catalyst for 0.5-24 hours in a reducing gas to obtain regenerated catalyst with activity fully recovered. An object of reuse of waste activated carbon generated in a production process of the glyphosate can be achieved by the method provided by the invention, thereby greatly reducing generation of solid waste in the production process of the glyphosate and simultaneously reducing production cost.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of renovation process of inactivation activated-carbon catalyst, be specifically related to a kind of renovation process that glyphosate is used activated-carbon catalyst for preparing.
Background technology
Glyphosate (chemical name: N-((phosphonomethyl)) glycine, English name: glyphosate) be the nonselective high-efficiency broad spectrum herbicide of interior suction after a kind of bud.Along with succeeding in developing and establishing in large scale of glyphosate genetically modified crops, and the popularization of the bio-fuel crop that causes of energy crisis, glyphosate becomes present global sales maximum and the fastest herbicide kind of growth rate.
The glyphosate synthesis route is numerous, and the route of international mainstream is imido oxalic acid method (being the IDA method), and its committed step is the PMIDA synthesizing glyphosate by catalytic oxidation.Hershman discloses in US3969398 take active carbon as catalyst, adopts oxygen-containing gas PMIDA to be oxidized to the method for glyphosate.Although this invention has lot of advantages, catalysqt deactivation is seriously its fatal weakness.To this, the application's applicant studies the preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid process, the activated centre of finding its catalytic process is that activated carbon surface contains pyridine and pyroles functional group, invented a kind of method of specific aim raising activated carbon surface pyridine and pyrroles's functional group content, be used for the glyphosate synthesis process, its catalytic activity is 2 times of US3969398 invention catalyst.Chinese patent has been applied in this invention, application number 201010578256.2.Although this catalyst life has good improvement, but still there is slow inactivation problem.
Usually, glyphosate producer solves the way of catalysqt deactivation and is: apply mechanically and constantly replenish the certain quantity of fresh catalyst in process and delay the life-span.The catalytic amount that this method consumes is larger, and along with applying mechanically increasing of number of times, in reactor, the content of solid glyphosate is more and more higher, cause the reactant liquor thickness, production efficiency descends, and the final solid waste that produces also increases thereupon, has increased simultaneously the operation cost in the glyphosate production process.
CN1150118A has introduced a kind of general renovation process of active carbon: carry out activating and regenerating take phosphoric acid as regenerative agent, the active carbon properties after activation is recovered.But this method is used for the inactivation activated-carbon catalyst regeneration of PMIDA catalytic oxidation, and poor effect still belongs to blank to the regeneration research of the inactivation activated-carbon catalyst of preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid both at home and abroad at present.
Summary of the invention
The object of the present invention is to provide a kind of renovation process that glyphosate is used activated-carbon catalyst for preparing.The present invention is studied for the preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid process especially, find the aobvious alkalescence of pyridine and pyrroles functional group of activated carbon surface, usually such active carbon pH value is between 8-13, with this catalyst as the PMIDA oxidizing process, highly acid reactant PMIDA is had very high absorption property, and this is convenient to the better contact catalyst Active sites of reactant; Simultaneously, pyridine and pyroles functional group have the effect that the selective oxidation tertiary amine changes into secondary amine.Therefore in the glyphosate synthesis process, the activated centre that pyridine and pyroles functional group serve as adsorption site and selective oxidation PMIDA simultaneously, the number of such functional group and catalytic performance are almost linear.Yet, in catalytic oxidation process, pyridine and pyroles functional group self are converted into the class amide group after removing carboxymethyl in PMIDA, make pyridine and the pyrroles functional group of aobvious alkalescence originally change into aobvious acid class amide groups, reduced on the one hand the ability of charcoal absorption PMIDA, the class amide groups that makes on the other hand the pyridine that possesses catalytic performance and pyrrole group change into non-activity, thus inactivation caused.
Based on above-mentioned deactivation mechanism, renovation process provided by the invention is set about from two aspects: the one, recover the absorption property of catalyst, and namely recover the alkalescence of catalyst; The 2nd, recover the catalyst surface active center, be about to the class amide groups and change into pyridine and pyroles functional group.Therefore, the renovation process of above-mentioned decaying catalyst focuses in the fracture of amido link, so long as be conducive to the method for the fracture of amido link, all can be used for the regeneration of this catalyst.The required condition of the fracture of known amido link is the existence of alkali, water, heat, so preparation glyphosate proposed by the invention is effective combination of alkali, water, hot three kinds of conditions with the core of catalyst recovery process.The experiment of wall scroll spare and many conditional combinations by above-mentioned renovation process can obtain the partially or completely catalyst of activity recovery.Catalyst after regeneration is consistent with the result of use of fresh catalyst, regeneration cost is far below newly purchasing catalyst, can greatly reduce solid waste and operation cost in glyphosate production process, thereby proposed the renovation process after a kind of preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid activated-carbon catalyst inactivation, realized purpose of the present invention.
Technical scheme of the present invention is as follows:
A kind of glyphosate for preparing comprises solvent elution and/or heat treatment step with the renovation process of activated-carbon catalyst, and each step method of operating is as follows:
1) solvent elution
Under 0.1-10Mpa pressure, adopt aqueous solution of inorganic matter and/or organic solvent to process inactivation activated-carbon catalyst 4-24h under reflux temperature, filtration washing is dried to constant weight to neutral; Described inorganic matter and organic solvent are the material with alkalescence or reproducibility;
2) heat treatment
Will through or the inactivation active carbon processed through solvent elution under inert atmosphere protection, be heated to 300-1500 ℃, pass into reducibility gas roasting 0.5-24h, then be cooled to room temperature in the inert atmosphere borehole cooling, rear activated-carbon catalyst obtains regenerating.
Described activated-carbon catalyst refers in particular to the activated-carbon catalyst of activated-carbon catalyst that preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid uses or noble metal, transition metal load.The activated-carbon catalyst of the activated-carbon catalyst of inactivation or complete deactivation or noble metal, transition metal load is divided in described inactivation activated-carbon catalyst finger.
So-called solvent elution and/or heat treatment step that the renovation process of activated-carbon catalyst of the present invention comprises, concrete meaning is: these two steps of solvent elution and heat treatment both can have been distinguished use separately, the catalyst of the two step operational processes inactivations that also can use in order as described above.According to the method described above, first step solvent elution regeneration efficiency can reach 0-60%; Second step thermal process regeneration efficient can reach 50-100%.
When using alkalescence or the reducing inorganic thing aqueous solution to process decaying catalyst, the aqueous solution of the hydroxide of preferred as alkali, alkaline-earth metal, ammonium, the sulfide of ammonium, carbonate or bicarbonate; Can select the aqueous solution of above-mentioned one or more inorganic matters to process the inactivation activated-carbon catalyst; The more preferably aqueous solution of the sulfide of the hydroxide of alkali metal, ammonium or ammonium.Pending inactivation activated-carbon catalyst and the mass ratio of inorganic matter are 1: 0.02-0.5, preferred 1: 0.05-0.2.The maximum regeneration efficient that this step is used separately can reach 50%.
When use possessed the organic solvent processing decaying catalyst of alkalescence or reproducibility, the organic solvent of alkalescence or reproducibility refered in particular to nitrogenous organic solvent; Preferred pyridines, pyroles, miazines, hydrazine class, amide-type or organic amine compound; Can select above-mentioned one or more organic solvents to process the inactivation activated-carbon catalyst; More preferably hydrazine class or amides compound.Pending inactivation activated-carbon catalyst and the mass ratio of organic solvent are 1: 1-10, preferred 1: 2-5.The maximum regeneration efficient that this step is used separately can reach 60%.
The solvent elution step also can be mixed use with the aqueous solution of above-mentioned inorganic matter with organic solvent, wherein not restriction of the ratio of the aqueous solution of inorganic matter and organic solvent.Catalyst through solvent elution is processed can be dried to constant weight according to a conventional method.For example in 80-150 ℃, be preferable over 100-120 ℃ of drying and get final product.
When using heat treating process to process decaying catalyst (it can be also to cross through the solvent elution step process that this catalyst both can be processed without solvent elution), described reducibility gas is selected from hydrogen sulfide, sulfur dioxide, nitric oxide, nitrogen dioxide, ammonia, carbon monoxide or hydrogen, preferred hydrogen sulfide; Described inert gas is selected from nitrogen, argon gas, helium or carbon dioxide, preferred nitrogen.The maximum regeneration efficient that this step is used separately can reach 100%.
In heat treatment step, further preferred operating condition is: sintering temperature 400-1200 ℃, and roasting time 1-12h.
Above-mentioned preparation glyphosate can carry out any combination and conversion with the treatment conditions described in the renovation process of activated-carbon catalyst and the inorganic agent of selecting, for example the solvent elution step both can select above-mentioned arbitrary material that decaying catalyst is processed, and also can select any two components or multicomponent to mix with arbitrary proportion and process.The user can be according to the concrete condition of pending decaying catalyst, determines to adopt renovation process provided by the present invention or only selects one of them in two steps.The most preferred assembled scheme of recommending exemplifies as follows:
(1) solvent elution: under refluxad, adopt hydrazine hydrate, after airtight stir process inactivation activated-carbon catalyst 4h, filtration washing is dried to constant weight to neutral;
(2) heat treatment: with the above-mentioned activated-carbon catalyst that is dried to constant weight under hydrogen sulfide atmosphere, 400 ℃ of constant temperature calcining 1h, the rear activated-carbon catalyst that obtains regenerating after cooling, heat treated intensification, temperature-fall period carry out under nitrogen atmosphere.
The present invention adopts regeneration efficiency to estimate the regeneration effect of decaying catalyst, evaluation test adopts following reaction condition to carry out the reaction that the PMIDA oxidation prepares glyphosate: in the 250mL autoclave, add 4.175g catalyst to be evaluated (i.e. catalyst after regeneration), 33.4g PMIDA and 100g water, 65 ℃ of reaction temperatures, partial pressure of oxygen 0.6Mpa, oxygen flow 150mL/min, speed of agitator 800rpm, reaction time 0.5h.After reaction finishes, filter, the pH value of reactant liquor is adjusted to 7, be settled to 500mL, HPLC analyzes content and the calculated yield (the rear catalyst yield of regenerating) of glyphosate.Same method adopts respectively fresh catalyst and decaying catalyst to prepare glyphosate, obtains respectively fresh catalyst yield and decaying catalyst yield.Calculate as follows the regeneration efficiency of catalyst:
The regeneration efficiency of calculating the inactivation activated-carbon catalyst of above-mentioned Optimum combinational scheme according to above method can reach 101%.
Preparation glyphosate provided by the invention has following advantage with the renovation process of activated-carbon catalyst:
1. regeneration cost is cheap, and far below the price of newly purchasing catalyst, the catalyst of holomorphosis is consistent with the fresh catalyst result of use, greatly reduces the production cost of glyphosate;
2. catalyst regeneration efficient is adjustable, is applicable to existing glyphosate producer and selects suitable, economic regeneration scheme according to pending catalyst;
3. solved and produced the solid waste problem in the prior art glyphosate production process, fundamentally solved the difficult problem that catalyst circulation is used.
The specific embodiment
Following examples are used for further illustrating the present invention, in order to better set forth content of the present invention.Following examples are only for example of the present invention clearly is described, and non exhaustive, are not also to be restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of following explanation.Everyly belong to apparent variation that technical scheme of the present invention extends out or change all within the spiritual scope that the present invention is contained.Wherein the inactivation activated-carbon catalyst is denoted as " De-AC ", and corresponding fresh catalyst is denoted as " Fr-AC " with it.
Embodiment 1 alkalescence or reproducibility organic solvent method of reproduction
Get 4 parts of each 100g of inactivation activated-carbon catalyst in 4 autoclaves, carry out solvent elution with pyridine, hydrazine hydrate, DMF, each 200g of ethylenediamine respectively.Treatment conditions: airtightly in autoclave be warming up to 170 ℃, after stirring 4h under the 500rpm rotating speed, filter after being down to room temperature, be washed to neutrality, 110 ℃ are dried to constant weight, obtain the regeneration activity Pd/carbon catalyst, are denoted as successively " Re-1-1, Re-1-2, Re-1-3, Re-1-4 ".Adopt preceding method that the regeneration effect of four regenerated catalysts is estimated, the results are shown in Table 1.
The regeneration effect of table 1 organic solvent to decaying catalyst
| Sample number into spectrum | Regenerative agent | Glyphosate yield/% | Regeneration efficiency/% |
| Fr-AC | - | 87.33 | - |
| De-AC | - | 37.37 | - |
| Re-1-1 | Pyridine | 62.50 | 50.30 |
| Re-1-2 | Hydrazine hydrate | 67.18 | 59.67 |
| Re-1-3 | DMF | 61.08 | 47.46 |
| Re-1-4 | Ethylenediamine | 40.77 | 6.81 |
Embodiment 2 alkalescence or reducing inorganic thing aqueous solution method of reproduction
Get 5 parts of each 100g of inactivation activated-carbon catalyst in 5 autoclaves, each 200g of the aqueous solution (each aqueous solution mass fraction is as 5%) take potassium hydroxide, sodium carbonate, carbonic hydroammonium, ammoniacal liquor, ammonium sulfide carries out solvent elution respectively.Treatment conditions obtain the regeneration activity Pd/carbon catalyst with embodiment 1, are denoted as successively " Re-2-1, Re-2-2, Re-2-3, Re-2-4, Re-2-5 ".Adopt preceding method that the regeneration effect of five regenerated catalysts is estimated, the results are shown in Table 2.
The regeneration effect of table 2 aqueous solution of inorganic matter to decaying catalyst
| Sample number into spectrum | Regenerative agent | Glyphosate yield/% | Regeneration efficiency/% |
| Fr-AC | - | 87.33 | - |
| De-AC | - | 37.37 | - |
| Re-2-1 | Potassium hydroxide | 67.09 | 59.49 |
| Re-2-2 | Sodium carbonate | 50.25 | 25.78 |
| Re-2-3 | Carbonic hydroammonium | 57.34 | 39.97 |
| Re-2-4 | Ammoniacal liquor | 59.27 | 43.84 |
| Re-2-5 | Ammonium sulfide | 68.84 | 63.00 |
The inorganic organic mixed solution method of reproduction of embodiment 3
Get inactivation activated-carbon catalyst 100g and drop into autoclave, add the ammonium sulfide solution 100g of 5% mass fraction, then add the 100g hydrazine hydrate; Separately get inactivation activated-carbon catalyst 100g and drop into autoclave, add the potassium hydroxide aqueous solution 100g of 5% mass fraction, then add the 100g DMF.Treatment conditions obtain the regeneration activity Pd/carbon catalyst with embodiment 1, are denoted as successively " Re-3-1 " and " Re-3-2 ".Adopt preceding method that the regeneration effect of two regenerated catalysts is estimated, the results are shown in Table 3.
The inorganic organic mixed solution method of reproduction regeneration effect of table 3
Embodiment 4 thermal process regenerations
Get 6 parts of each 100g of inactivation activated-carbon catalyst and put into respectively 6 quartz boats; 5 ℃/min speed is warming up to 1000 ℃ under the inert nitrogen gas protection; pass into respectively hydrogen sulfide, sulfur dioxide, nitric oxide, carbon monoxide, hydrogen, the ammonia of 100mL/min; 1000 ℃ of constant temperature calcining 1h; obtain the regeneration activity Pd/carbon catalyst after being down to room temperature, be denoted as successively " Re-4-1, Re-4-2, Re-4-3, Re-4-4, Re-4-5, Re-4-6 ".Adopt preceding method that the regeneration effect of six regenerated catalysts is estimated, the results are shown in Table 4.
The hot method of reproduction regeneration effect of table 4 different atmosphere
| Sample number into spectrum | Regeneration atmosphere | Glyphosate yield/% | Regeneration efficiency/% |
| Fr-AC | - | 87.33 | - |
| De-AC | - | 37.37 | - |
| Re-4-1 | Hydrogen sulfide | 76.92 | 79.16 |
| Re-4-2 | Sulfur dioxide | 68.88 | 63.07 |
| Re-4-3 | Nitric oxide | 87.27 | 99.88 |
| Re-4-4 | Carbon monoxide | 76.34 | 78.00 |
| Re-4-5 | Hydrogen | 68.89 | 63.09 |
| Re-4-6 | Ammonia | 70.32 | 65.95 |
Embodiment 5 mixed regeneration methods
Getting 6 parts of inactivation activated-carbon catalyst 100g processes through following steps respectively:
1) respectively get the 200g hydrazine hydrate and add and airtightly in autoclave be warming up to 170 ℃, stir 4h under the 500rpm rotating speed, filter after being down to room temperature, 110 ℃ are dried to constant weight;
2) above-mentioned dried sample is put into respectively 6 quartz boats; 5 ℃/min speed is warming up to 400 ℃ under the inert nitrogen gas protection; pass into respectively the atmosphere such as hydrogen sulfide, sulfur dioxide, nitric oxide, carbon monoxide, hydrogen, ammonia of 100mL/min; 400 ℃ of constant temperature calcining 1h; obtain regenerated carbon after being down to room temperature, be denoted as successively " Re-5-1, Re-5-2, Re-5-3, Re-5-4, Re-5-5, Re-5-6 ".Adopt preceding method that the regeneration effect of six regenerated catalysts is estimated, the results are shown in Table 5.
Table 5 mixed regeneration method regeneration effect
| Sample number into spectrum | Renovation process | Glyphosate yield/% | Regeneration efficiency/% |
| Fr-AC | - | 87.33 | - |
| De-AC | - | 37.37 | - |
| Re-5-1 | Hydrazine hydrate+hydrogen sulfide | 88.28 | 101.90 |
| Re-5-2 | Hydrazine hydrate+sulfur dioxide | 86.95 | 99.24 |
| Re-5-3 | Hydrazine hydrate+nitric oxide | 87.34 | 100.00 |
| Re-5-4 | Hydrazine hydrate+carbon monoxide | 85.29 | 95.92 |
| Re-5-5 | Hydrazine hydrate+hydrogen | 87.74 | 100.82 |
| Re-5-6 | Hydrazine hydrate+ammonia | 86.76 | 98.86 |
Claims (7)
1. one kind prepares glyphosate with the renovation process of activated-carbon catalyst, comprises solvent elution and/or heat treatment step, and each step method of operating is as follows:
1) solvent elution under 0.1-10Mpa pressure, adopts aqueous solution of inorganic matter and/or organic solvent to process inactivation activated-carbon catalyst 4-24h under reflux temperature, and filtration washing is dried to constant weight to neutral; Described inorganic matter and organic solvent are the material with alkalescence or reproducibility;
2) heat treatment will through or the inactivation active carbon processed through solvent elution under inert atmosphere protection; be heated to 300-1500 ℃; pass into reducibility gas roasting 0.5-24h, then be cooled to room temperature in the inert atmosphere borehole cooling, rear activated-carbon catalyst obtains regenerating.
2. according to renovation process claimed in claim 1, it is characterized in that: step 1) described in inorganic matter be selected from one or more in following material: the hydroxide of alkali metal, alkaline-earth metal, ammonium, the sulfide of ammonium, carbonate, bicarbonate; Consumption is pending inactivation activated-carbon catalyst and the mass ratio 1 of inorganic matter: 0.02-0.5.
3. according to renovation process claimed in claim 2, it is characterized in that: step 1) described in aqueous solution of inorganic matter be selected from the aqueous solution of the sulfide of the hydroxide of alkali metal, ammonium or ammonium; Consumption is pending inactivation activated-carbon catalyst and the mass ratio 1 of inorganic matter: 0.05-0.2.
4. according to renovation process claimed in claim 1, it is characterized in that: step 1) described in organic solvent be selected from one or more in following material: pyridines, pyroles, miazines, hydrazine class, amide-type, organic amine compound; Consumption is pending inactivation activated-carbon catalyst and the mass ratio 1 of organic solvent: 1-10.
5. according to renovation process claimed in claim 4, it is characterized in that: step 1) described in organic solvent be selected from hydrazine class or amides compound; Consumption is pending inactivation activated-carbon catalyst and the mass ratio 1 of organic solvent: 2-5.
6. according to renovation process claimed in claim 1, it is characterized in that: step 2) described in reducibility gas be selected from hydrogen sulfide, sulfur dioxide, nitric oxide, nitrogen dioxide, ammonia, carbon monoxide or hydrogen; Described inert gas is selected from nitrogen, argon gas, helium or carbon dioxide.
7. according to renovation process claimed in claim 6, it is characterized in that: step 2) described in reducibility gas be selected from hydrogen sulfide; Described inert gas is selected from nitrogen.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080521A (en) * | 2015-08-07 | 2015-11-25 | 浙江奇彩环境科技有限公司 | Activated carbon regeneration method |
| CN106512974A (en) * | 2016-11-10 | 2017-03-22 | 中南大学 | Regeneration method of activated carbon |
| CN108212135A (en) * | 2017-12-29 | 2018-06-29 | 南通泰禾化工股份有限公司 | The recycling and processing device and method of dead catalyst in a kind of Bravo synthesis technology |
| CN108722500A (en) * | 2018-07-03 | 2018-11-02 | 辽宁格瑞凯特科技有限公司 | Glyphosate cleans recycling method after being inactivated with activated-carbon catalyst |
| CN108906138A (en) * | 2018-07-04 | 2018-11-30 | 成都恩承科技股份有限公司 | A kind of regeneration method of active carbon or carbon-supported catalysts |
| CN111432911A (en) * | 2017-10-01 | 2020-07-17 | 艾博森有限公司 | Method of recycling saturated active sorbent of a filter module |
| CN113262757A (en) * | 2021-06-01 | 2021-08-17 | 上海市固体废物处置有限公司 | Method for preparing furfural while regenerating waste activated carbon |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080521A (en) * | 2015-08-07 | 2015-11-25 | 浙江奇彩环境科技有限公司 | Activated carbon regeneration method |
| CN106512974A (en) * | 2016-11-10 | 2017-03-22 | 中南大学 | Regeneration method of activated carbon |
| CN111432911A (en) * | 2017-10-01 | 2020-07-17 | 艾博森有限公司 | Method of recycling saturated active sorbent of a filter module |
| CN108212135A (en) * | 2017-12-29 | 2018-06-29 | 南通泰禾化工股份有限公司 | The recycling and processing device and method of dead catalyst in a kind of Bravo synthesis technology |
| CN108722500A (en) * | 2018-07-03 | 2018-11-02 | 辽宁格瑞凯特科技有限公司 | Glyphosate cleans recycling method after being inactivated with activated-carbon catalyst |
| CN108906138A (en) * | 2018-07-04 | 2018-11-30 | 成都恩承科技股份有限公司 | A kind of regeneration method of active carbon or carbon-supported catalysts |
| CN113262757A (en) * | 2021-06-01 | 2021-08-17 | 上海市固体废物处置有限公司 | Method for preparing furfural while regenerating waste activated carbon |
| CN113262757B (en) * | 2021-06-01 | 2022-07-26 | 上海市固体废物处置有限公司 | Method for preparing furfural simultaneously by regenerating waste activated carbon |
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